U.S. patent number 5,174,859 [Application Number 07/683,244] was granted by the patent office on 1992-12-29 for method for treating mechanical pulp plant effluent.
This patent grant is currently assigned to HPD Incorporated. Invention is credited to Jean-Claude Patel, Timothy J. Rittof.
United States Patent |
5,174,859 |
Rittof , et al. |
December 29, 1992 |
**Please see images for:
( Certificate of Correction ) ** |
Method for treating mechanical pulp plant effluent
Abstract
A method for treating a mechanical pulp plant effluent waste
stream by freezing the effluent stream and separating frozen
product. The frozen product contains between about 50 to 150 ppm
chemical oxygen demand (COD), and may be reclaimed.
Inventors: |
Rittof; Timothy J. (Lombard,
IL), Patel; Jean-Claude (Aurora, IL) |
Assignee: |
HPD Incorporated (Naperville,
IL)
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Family
ID: |
27056070 |
Appl.
No.: |
07/683,244 |
Filed: |
April 10, 1991 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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508041 |
Apr 11, 1990 |
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Current U.S.
Class: |
162/29;
159/DIG.5; 162/189; 162/54; 210/774; 62/541 |
Current CPC
Class: |
C02F
1/22 (20130101); D21C 11/0042 (20130101); Y10S
159/05 (20130101) |
Current International
Class: |
C02F
1/22 (20060101); D21C 11/00 (20060101); B01D
009/04 () |
Field of
Search: |
;162/29,42,43,54,189
;210/774 ;159/DIG.5 ;62/532,541,542 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Davis, Harold E.; Egan, Christopher J., "Use of Freeze
Concentration Technology In Black Liquor Evaporation"; American
Institute of Chemical Engineers Symposium Series, 1981, pp. 50-56.
.
Heist, James A., "Freeze Crystallization Applications for
Waste-water Recycle and Reuse"; American Institute of Chemical
Engineers Symposium Series, 1981, pp. 259-272. .
Rousseau, Ronald W.; Sharpe, Emerson E., "Freeze Concentration of
Black Liquor: Characteristics and Limitations"; Industrial
Engineering Chemical Process Design Development, 1980, pp. 201-204.
.
Wiley, A. J.; Dambruch, Lyle E.; Parker, Peter E.; Dugal, Hardev S.
"Treatment of Bleach Plant Effluents: A Combined Reverse
Osmosis/Freeze Concentration Process"; Tappi Journal, Dec. 1978,
pp. 77-80..
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Primary Examiner: Jones; W. Gary
Assistant Examiner: Friedman; Charles K.
Attorney, Agent or Firm: Willian Brinks Olds Hofer Gilson
& Lione
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATION
This is a continuation in part of application Ser. No. 508,041,
filed Apr. 11, 1990, now abandoned.
Claims
We claim:
1. A process for producing high purity water from a mechanical pulp
plant effluent waste stream and recycling said water to the
mechanical pulping process, said process comprising:
a) indirectly cooling the effluent stream to a temperature near the
freezing point of the stream;
b) crystallizing a portion of the effluent stream to obtain a
frozen product and a liquid concentrate;
c) separating the frozen product from the liquid concentrate;
and
d) recovering and recycling a portion of the frozen product to the
mechanical pulping process.
2. The method of claim 1 where the frozen product is separated from
the liquid concentrate by gravity.
3. The method of claim 1 further comprising recycling the separate
frozen product to the pulping process.
4. The method of claim 1 further comprising recycling at least a
portion of the separated liquid concentrate to the effluent waste
stream.
5. The method of claim 1 where the separated liquid concentrate is
further concentrated by evaporation.
6. The method of claim 1 where the separated liquid concentrate is
incinerated.
7. The method of claim 1 where the effluent waste stream comprises
SGW, PGW, TMP, CTMP, BCTMP, or APMP plant effluent waste
streams.
8. The method of claim 1 where the frozen product comprises
crystalline water.
9. The method of claim 1 where the frozen product contains between
about 50 to 150 ppm COD.
10. A method for treating a mechanical pulp plant effluent waste
stream and recycling a portion of the stream to the mechanical
pulping process, said process comprising:
a) cooling the effluent stream by indirect means to a temperature
near the freezing point of the stream;
b) crystallizing the cooled effluent stream to obtain a crystalline
water product and a liquid waste concentrate;
c) separating the crystalline water product from the liquid waste
concentrate; and
d) recovering and recycling a portion of the crystalline water
product to the mechanical pulping process.
11. The method of claim 10 wherein the crystalline water product is
concentrated during separation and washing.
12. The method of claim 10 further comprising melting the
crystalline water product after the product is washed.
Description
BACKGROUND OF THE INVENTION
The invention relates to the treatment of mechanical pulp waste
effluent. More specifically, the invention relates to the
application of freeze crystallization to purify mechanical plant
effluent waste streams and to reclaim high purity water.
Mechanical pulp plant mills discharge waste streams which contain
unacceptable quantities of contaminants such as inorganic salts,
wood waste, organic materials, and volatile gases. The contaminants
are commonly removed by concentrating the waste stream and
separating the reclaimed effluent. Evaporation is a common
concentration technique.
In evaporation, heat is applied to the waste stream to distill the
reclaimed water. The heat, however, also distills contaminating
organics and gases with the water. These contaminants are
unacceptable, and secondary treatment of the distillate is
necessary to recover high purity water. Thus, process water can be
reclaimed only after these contaminants are removed from the
distillate. After secondary treatment, reclaimed water can then be
recycled to the pulping process, used in other processes, or
discharged back to the environment.
It has been found, however, that mechanical pulp waste streams may
be sufficiently concentrated by freezing the effluent. After
freezing and separation, the resulting reclaimed water effluent is
substantially higher in quality than the distillate from an
evaporating process. Thus, the frozen reclaimed water effluent
requires only minimal or no secondary treatment.
Accordingly, one advantage of the invention is that distillation of
contaminants is avoided, thereby allowing high purity water to be
recovered from mechanical pulp plant effluents. Further, the
chemical oxygen demand (COD) in the reclaimed water may be brought
down to zero more economically than known before. Also, low
temperature treatment of the waste effluent reduces or eliminates
corrosion of vessels and pumps experienced in the high temperature
evaporator process.
SUMMARY OF THE INVENTION
The present invention provides a method for treating a mechanical
pulp plant effluent waste stream by freezing the effluent stream
and separating frozen product. In one embodiment, the mechanical
pulp plant effluent waste stream is frozen to obtain a crystalline
water product and a liquid waste concentrate. The crystalline water
product may be reclaimed by washing away the liquid waste
concentrate.
In another embodiment, the method contemplates indirectly cooling
the mechanical pulp effluent waste stream and then crystallizing
the cooled water to obtain a slurry containing a frozen product and
a concentrate. The frozen product is separated from the
concentrate, washed and then melted to obtain a high purity
liquid.
In another embodiment, the method contemplates recycling at least a
portion of the waste concentrate to the waste effluent stream.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a process schematic of one embodiment of the present
invention.
FIG. 2 is a process schematic of another embodiment of the present
invention.
DETAILED DESCRIPTION OF THE DRAWINGS AND PREFERRED EMBODIMENTS
The method of this invention may be applied to any effluent waste
stream emitted by a mechanical pulp plant. Such mechanical pulp
plants include those which primarily use mechanical energy to
separate wood fibers from the wood matrix. Thus, mechanical pulp
effluent waste includes waste generated from stone ground wood
(SGW), pressurized ground wood (PGW), thermomechanical pulp (TMP),
chemical thermomechanical pulp (CTMP), bleach chemical
thermomechanical pulp (BCTMP), alkaline peroxide mechanical pulp
(APMP), and like processes where the pulp yield is high and the
amount of waste is relatively small.
Mechanical pulp effluent waste streams typically contain waste
materials present in the wood stock fed to the process and any
chemicals used in softening or processing the wood. These effluents
are complex and very difficult to characterize, and are therefore
customarily defined in the industry by their process source.
Without limiting the invention, such wood waste may contain, for
example, organic acids, volatile organics, resinous compounds, and
lignins. Chemicals commonly used in a mechanical pulp process
include inorganic salts such as sodium sulfite, sodium hydroxide,
and sodium carbonate. The wood waste and process chemicals
contaminate the mechanical pulp effluent, creating high saline,
chemical oxygen demand (COD), and biological oxygen demand (BOD)
levels. These waste materials may also make the waste stream toxic.
Other wood waste and chemical contaminants, known to those skilled
in the art but not mentioned here, are also contemplated.
In accordance with one embodiment, the mechanical pulp effluent
waste treated by the present invention contains inorganic
contaminants, such as salts, and organic contaminants. The organic
materials include heavy organics, such as lignins, fatty acids,
carbohydrates, and light organics, such as methanol. The mechanical
pulp effluent waste treated by the invention typically contains
high amounts of volatile organics, and preferably between about 0.1
to 2.0 percent by weight. These volatile organics generally have a
boiling point between about 150 to 220.degree. F. (65 to
104.degree. C.) at ambient conditions and include, for example,
volatile acids.
According to the process, the mechanical pulp waste effluent is
treated at or near the freezing point, about 0 to 30.degree. F.
(-17 to -1.degree. C.), at ambient pressures. Preferably, the waste
effluent is treated between about 10 to 25.degree. F. (-12 to
-6.degree. C.). The lower temperature parameter is limited by the
freezing potential of the effluent as it moves through the
equipment, such as the ice column. For example, the lower
temperature may be limited by the freezing potential of the
material during the washing step. Thus, the lower limit may be
below 0.degree. F. as long as the material being treated does not
freeze or jam the equipment or otherwise obstruct the process.
One embodiment of the invention is shown in FIG. 1. In this
embodiment, waste effluent is first pretreated. In this case, the
effluent in line 1 is pretreated in clarifier 2, but any
pretreatment step known in the art is suitable. Pretreatment is not
necessary to the process, but is employed to reduce high amounts of
suspended solids in the waste effluent.
The pretreated effluent is pumped through line 3 to freezer 4,
where a slurry containing a frozen product and a liquid concentrate
is formed. The feed to the freezer 4 preferably contains no greater
than 10 percent by weight total solids. As used herein, the term
total solids means the sum of dissolved solids and suspended
solids. Preferably, the feed contains total solids between about
1000 ppm to 10 percent by weight.
The product and concentrate are formed between the temperature
range of about 0 to 32.degree. F. (-17 to 0.degree. C.) at
atmospheric pressures. Preferably, the frozen product comprises
crystalline water, or ice, and the liquid concentrate contains the
contaminants. The crystalline water may contain between about 50 to
150 ppm chemical oxygen demand (COD). The crystalline water
generally also may contain between about 50 to 150 ppm total
dissolved solids (TDS).
The frozen product is then separated from the liquid concentrate.
In this embodiment, the slurry is pumped through line 5 to washer 6
where the ice is washed by mechanical means with water under
conditions to maintain the crystallinity. The ice, however, may be
separated by any means known in the art including filtration and
centrifugation. The ice is recovered, reused in the plant,
including the pulping operation, or returned to the water
source.
In this embodiment, a portion of the separated liquid concentrate
is recycled in line 7 to line 3 which feeds freezer 4. The
separated liquid concentrate may, of course, be recirculated in any
amount sufficient for the process, and may be fed to any sufficient
point, such as directly to the freezer. The contaminants in the
remaining portion of separated liquid concentrate may be disposed
of in any manner known in the art. In this instance, the liquid
concentrate is fed through line 8 to evaporator 9 to further
concentrate the contaminants. The contaminants are then burned in
incinerator 10.
FIG. 2 illustrates another embodiment of the invention employing a
continuous freezing process which forms an ice slurry. Waste
effluent 20 is fed to freezer 21 which employs an indirect freezing
process. Indirect freezing processes which may be employed are
described in U.S. Pat. Nos. 4,286,436; 4,335,581; 4,457,769;
4,532,985, the teachings of which are incorporated herein. Here,
freezer 21 contains a heat exchange section 22 and a slurry
retention chamber 23. The heat exchange section 22 comprises tubes
24 and a shell 25, thereby forming a shell and tube heat exchanger.
Refrigerant is fed to the shell in line 26 and returns to condenser
28 through line 27. The refrigerant may be any commonly employed
refrigerant, such as ammonia or freon. While a shell and tube
exchanger is illustrated here, any indirect cooling process is
contemplated, including those described in the previously mentioned
patents. Moreover, any acceptable refrigeration process, such as
recirculating systems and pool boiling systems, may be
employed.
Waste effluent is cooled within the tubes 24 close to the freezing
point. Pump 29 recycles liquid back through the tubes 24 from the
slurry retention chamber 23 through line 30. In this embodiment,
frozen product does not form in the tubes 24, but instead forms in
the slurry retention chamber 23. The frozen product preferably
forms in chamber 23 by crystallizing upon contact with solid
material which is present in the chamber. The solid material
functions as a crystallizing seed and is preferably the frozen
product of the slurry. During start-up, an appropriate seed
material may be used to initiate crystallization of the frozen
product. High purity crystalline water is preferred as a
crystallizing seed.
The temperature in the slurry chamber 23 is preferably maintained
at a temperature which will allow the above continuous freezing
process to be carried out without hindrance. Preferably, the
temperature is maintained between about 0 and 30.degree. F. (-17
and 1.degree. C.), more preferably between about 10 and 25.degree.
F. (-12 and -6.degree. C.), and most preferably at the freezing
point of the material. The slurry preferably contains between about
3 to 30 percent by weight of high quality ice, with the remaining
portion being the liquid fraction. The liquid fraction, also known
as the mother liquor, preferably contains between about 8 and 40,
and most preferably between about 10 and 15, percent by weight
total solids, with the remainder being water.
The slurry from the chamber 23 is fed through line 31, at a
temperature of about 10.degree. to 25.degree. F. (-12.degree. to
-6.degree. C.), and preferably at about 23.degree. F. (-5.degree.
C.), to a washer column 32. The washer column 32 may be any
suitable design, such as a gravity or a hydraulic piston design.
Here, washer column 32 is a gravity design and contains a
separation chamber 33, a washing chamber 34 and an annular melting
chamber 35. The slurry is continuously fed to an inlet located near
the bottom of the separation chamber 33, and the slurry travels
upwardly into the washing chamber 34. The slurry concentrates as it
proceeds upwardly, and preferably reaches a concentration in the
washing chamber of about 75 to 90 percent by weight of high quality
ice.
Wash liquid, which may be pure or recycled high quality water, is
added to the top of the washer column 32 from line 36 and
distributor 37. In the washer column 32, the wash liquid flows
downwardly as the ice pack rises to the top of the washing chamber
34. At the top of the washing chamber 34, the ice pack is fed into
by the annular melting chamber 35. The ice pack may be transferred
to the melting chamber by any suitable transfer means, such as a
rotating mechanical scraping blade 38.
The melting chamber 35 converts the high quality crystalline ice to
high quality liquid water, and is preferably maintained at
temperature of about 32.degree. F. (0.degree. C.). In accordance
with FIG. 2, the high quality water is fed to condenser 28 through
line 39 and there heat exchanged with the refrigerant. The heat
exchanged high quality water is then reclaimed from line 40, and
can be recycled to the pulping process, returned to the
environment, or used in other processes as shown in FIG. 1.
Concentrate is drawn in line 42 from the separator chamber 33 and
may recycled to the treating process or disposed of by evaporation
or incineration, as illustrated in FIG. 1. The concentrate contains
the contaminants which were present in the mechanical pulp plant
effluent waste, including the volatile organics and heavy organics
mentioned earlier.
Thus, the present invention employs a freeze separation technique
for a mechanical pulp plant effluent waste stream that removes both
volatile and heavy organics in the concentrate and yields a high
quality reclaimable water. Moreover, when indirect freezing is
employed, the volatile organics are prevented from contaminating
the refrigerant. These and other advantages are illustrated in the
examples.
EXAMPLES
Mechanical pulp plant effluent wastes having the compositions given
in Table 1 were treated. Each effluent was fed to a continuous
indirect freezer containing a shell and tube heat exchanger and
slurry chamber. The slurry chamber was maintained at a temperature
of about 25.degree. F. (-6.degree. C.), and the slurry contained 5
percent by weight ice. The slurry was fed to a washer column
containing a separation chamber, a washing chamber and a melt
chamber. High quality ice was collected from the washing chamber
and melted in the melting chamber at a temperature of 34.degree. F.
(1.degree. C.). The resulting high quality water in tests 1 to 5,
contained between 10 to 100 ppm COD and averaged about 50 ppm COD.
Concentrate was drawn from the bottom of the separation chamber and
had the composition shown in Table 2.
TABLE 1
__________________________________________________________________________
TYPICAL WASTE FEED ANALYSIS ANALYSIS 1 2 3 4 5
__________________________________________________________________________
pH 10.2-10.5 8.4-8.8 6.1-6.4 6.3-7.6 5.7-6.8 Conductivity 8550 8500
5250 12000 7000 Density 1.02 1.02 1.02 1.015 0.0998 Total Solids
(%) 1.33 1.98 1.16 2.6 1.88 Ash (% of TS) 48.1 37.5 36.1 40.1 32.5
Suspended Solids (ppm) 150 5390 1550 1750 2741 C.O.D. (ppm) 10000
18000 10000 28000 15000 T.O.C. (ppm) 3715 7863 3825 10200 5100
Volatile Acids (ppm) 4193 13826 9466 9060 5960 Carbonate (ppm) 1884
756 616 Sulfate (%) 0.04 0.12 0.09 1386 1340 Sulfide (ppm) 95 142
0.002 Chloride (ppm) 15 65 48 Sodium (ppm) 2822 3011 1550 3700 2000
Calcium (ppm) 55 68 105 101 184 Potassium (ppm) 13 27 155 60 42
Magnesium (ppm) 102 67 105 63 34 Aluminum (ppm) 8.1 1.7 <1 <5
<5 Silicon (ppm) 156 171 749 570 0
__________________________________________________________________________
TABLE 2 ______________________________________ CONCENTRATE
COMPOSITIONS COMPONENT 1 2 3 4 5
______________________________________ Total Solids % 9.5 10.5 --
14.5 -- C.O.D. % 7.14 9.54 -- 15.6 --
______________________________________
The invention is not intended to be limited by the above preferred
embodiments. Its full scope, however, is defined by the appended
claims.
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